Seed dressing agents employing a



Patented June 3, 1947 p SEED DRESSING AGENTS EMPLOYING A HYDROXY PHENYL POUND DIAZONIUM COM- Wilhelm Bonrath, Leverkusen I. G.-Werk, and Ewald Urbschat, Cologne-Mulheim, Germany; vested in the Attorney General of the United States No Drawing. Application March 29, 1943, Serial No. 481,010. In Germany October 10, 1940 6 Claims. 1

This invention relates to a-fungicidal preparation.

As seed dressing agents generally organic mercury compounds are used which are distinguished by an excellent fungicidal efficacy. Nevertheless, these compounds possess certain disadvantages in that they are all rather toxic and sometimes prevent germination of the seed. For these reasons, it has been attempted to replace such mercury compounds at least in part in seed dressing agents. As mercury-free fungicidal preparations hydroxyphenylhydrazines have recently been suggested. Thesecompounds possess a very good fungicidal efficacy especially against winged blight of oats. If, however, they are stored in admixture with mercury or copper compounds, these heavy metal compounds are reduced, whereby the eflicacy of the mixture decreases. Since such mixtures are of great practical importance, this reducing property of the hydroxyphenylhydrazines hampers their practical use. Also double salts of aromatic diazonium salts, in which the aromatic nucleus may be substituted,

for instance, by alkyl, nitro or halogen atoms,

mercuric chloride, which they contain, is toxic they are not suited for combatting winged blight of oats.

We have now found that aromatic diazo com- A pounds which contain besides the diazo group phenols or naphthols.

described may be used'which are derived from One or several hydroxyl groups may be present. The diazo group and the phenolic hydroxyl group may be substituents to the same or to different rings. Such compounds which contain both groups as substituents of r the same ring have proved to be particularly efligroups. They may be further substituted by pchloroalkyl, phenylmethyl, chlorophenyl or cchloroethoxy radicals or by the -CH2COO.C2I- I5 group. Also sulfone, sulfoxide, carboxylic acid, carboxyalkyl (for instance carboxymethyl or carboxyethyl radicals), arsine oxide radicals or halogen atoms, such as bromine or chlorine, may be substituents to the ring.

In the grouping (NN) both nitrogen atoms may be trivalent (N=N) or one of them may be pentavalent (*F Thus, the diazo group may be functionally intact as in the case of diazonium salts, diazotates.

-diazo double salts or diazo sulfonates, or the the second valency of which is bound to a radithat of the hydroxyphenylhydrazines; they show the further advantage that they may be stored preparations.

in mixture with metal salts without'chemically changing the same.

The said compounds correspond to the general formula [HOAr(NN) lY Ar designates therein an arylene radical, NN is Itis to be seen therefrom that Y preferablythe diazo group; Y is an inorganic or organic radical other than a hydrocarbon residue.

The hydroxyl or the diazo group may be bound to a monoor polycyclic aromatic ring system. i

For instance, diazo compounds ofthe character diazo function may have disappeared as it is the case with the diazoamino or diazoimino compounds. As diazo components in the compounds to be used according to our invention, there may be cited, for example, the following groups:

(Me=metal, X=monovalent acid radical, R: eventually substituted hydrocarbon radical.)

stands either for metal salt which is capable of forming complex salts or an inorganic or organic radical derived from an acid or base.

In the said compounds, the diazo group may mbe stabilized by chemical means in the known 3 manner or by admixture with inert materials such as sodium sulfate.

The following compounds are by way of example suitable for the purpose of our invention:

(11) 3,5 dichloro-4-hydroxyphenyldiazopyrollidide, (12) 3,5 dichloro-4-hydroxyphenyldiazopiperidide.

As fungicidal preparations, the said compounds may be used in the usual manner, for instance as dry, wet or oil seed dressing agents. They may also be used in the form of oily emulsions. For the preparation of a dry seed dressing agent, they are admixed with solid inert carriers, for instance chalk, kieselguhr, slate flour or talc. As wet seed dressing agents, they are, dissolved in water, for instance in the form of their alkali metal salts. Also oily solutions may be prepared, if necessary by means of a solubilizer.

For fungicidal purposes, the said compounds.

may be used either alone or together with, other fungicides, for instance, organic mercury compounds, such, as phenylmercury-acetate, methoxyethyl-mercury-silicate or 'chloride or ethylmercury-chloride. Such mixtures, have proved to be of special importance, since they have an excellent fungicidal'efii'cacy against all plant diseases conveyable by the seed grain, though they may contain less mercury than the known prep.- arations which are now on the market. The-arumatic diazo compounds of the character described are in general best suited for combatting the winged blight of oats. They may. therefore readily be combined with mercury compounds which as a rule are most efficacious against fusarium of rye, but less active against. winged blight. of oats.

The mercuric chloride double salts of the hydroxyphenyl'diazonium compounds to be used according to our invention are much more active against winged blight of oats. than the known seed dressing agents which contain double salts of aromatic diazonium salts and mercuric chloride as active ingredients. If, for instance, seed grain is treated with a preparation containing 9% of mercury as the double salt of phenyldiazoniumchloride and mercuric chloride in the amount of 41000; still 12.3% of the seedlings are attacked by winged blight of oats, whereas, if a batch of the same seed grain is treated with the double salt of p-hydroxyphenyldiazoniumchloride and, mercuric chloride in the same concentration of mercury in the amount of only 3:1,000, 0.9% of the seedlings are: attacked. With theuntreated seed grain, the. attack was 25.9%.

Our inventionv is furthermore illustrated by the. following examples Without, however. being limited'thereto, the'parts being by weight:

EXAMPLE 1 Preparation 1 25 parts of potassium 4-hydroxyphenyldiazosulfonate+75 parts of talc,

Preparation 2 (a) 30 parts of sodium l-hydroxy-n-methylbenzene-4-diazosulfonate+70 parts of talc,

(b) 20 parts of sodium 1-hydroxy-2-methylbenzenel-diazosulfonate+ parts of talc,

Preparation 3 10 parts of potassium 4-hydroxyphenyl-diazosulfonate+1% of mercury as phenylmercuryacetate; rest=inert material,

Preparation 4 30 parts of sodium 1-hydroxy-3-chlorobenzene--diazosulfonate+l0 parts of talc,

Preparation 5 30 parts of 2 ,6-dichlorophenol-4-diazooxide+70 parts of inert material,

Paration 6:

30 parts of 2,6-dichlorophenol-4-diazopiperie dide+70 parts of inert material,

Preparation 7 30. parts of l-hydroxy-benzene-a-diazoferricyanide+70i% of talc,

Preparation 8 30 parts of 1-hydroXy-2-chloro-benzene-4-d1- azo- (3'-ch1oro-4'-hydroxy- 5'-nitro-benzene -sul.- fonate+70 parts of inert material,

Preparation 9 30 parts of 1-hydroxy-benzenee4-diazo-borofiuoride+70 parts of inert. material.

(a) Fusariam of the rye TEST I Amountof I 1 preparation: 111 plants. I g amount of in'per cent p n I Seed grain per cen Preparation l 2:1000 0.6. l 79. Preparation 2a.- 2:1000 0.6 77.3 Untreated seeds 17 52. 3

TEST II.

' Amountofi preparation: 111 plants g f; amount of in per cent" D an S t l seed grain per can Preparation 8 o 2: 1000; 0. 3. 50. 3 1 5:10)... 2.3. 49- Preparation 9; 22-1000 0' 47:6. 1 5:1000, 1.3. .45. Untreatedseeds 19. 20.3

(b) Winged blight a; oats TEST I I Proportion. g gf Preparation 1. 2:1000. 0 Preparationfla,- (l Preparation3 0 Untreated seeds 58. 5.

: TE T H Proportion gl gf Preparation 2b 2: 1000 1 5:1000 0 Preparation 4 2: 1000 0 V 1 511000 0 25 Preparation 7 2:1000 0 l 5:1000 0.6 Untreated seeds 3.9 10

(0) Stone blight of barley Germination Proportion of the spores Preparation 1:1000 0 Preparation 3. 1 :1000 0 Preparation 4. 121000 0 Preparation 5. 1:1000 0 Preparation 6 121000 0 Untreated seeds 20 a (d) Stone blight of wheat Germination Proportion of the spores 2 Preparation 3 2:1000 0 Preparation 4 211000 0 Preparation 5 2: 1000 0 Preparation 6 .s 2: 1000 0 Untreated seeds EXAMPLE 2 In an experimenton the field, the following results were obtained when combatting the strip disease of barley and while using the dry seed dressing agents cited below:

Preparation Proportion Attacked Percent 1 Untreated seeds 16. 2 20% of potassium 1-hydroxy-2-methy1- benzene-4-diazosu1tonate, 80% of talc. 2:1000 0 3 30% of sodium l-hydroxy-Z-chlorobenzene--diazosulfonate, 70% of talc- 2:1000 0.25 4 30% of sodium l-hydroxy-3-ohlorobenzene--diazosulfonate, 70% ottalc- 2:1000 0 5 30% of l-hydroxy-benzenei-dlazoiperidide, 70% of talc 2:1000 0. 25 6 1'7? of mercury as methoxyethylmercury silicate, 10% of sodium 1- hydroxy-2-ehloro-benzene-4-diazosulfonate 2:1000 0 Rest (calculated on 100%)=ta1c 1 5:1000 0 EXAMPLE 3 Seed grains of rye, attacked by fusarium, are dipped for minutes into 0.1 or 0.2% solutions of the following compounds. The results of 3 different series of experiments are resumed in the following table:

First series of experiments 6 Healthy lllplants 0.1% solutions plants in in per per cent cent 1 H20 27.3 17.3 2 Sodium 1-hydroxy-2-chloro-benzene+dia- 3 zosul fonate 66 0 63.6 o 7 5 l-hydroxy-phenyl-i-d benzene-Y-sulionato) 57 0 6 l-hydroxy-phenyli- Zene-Y-SuIfonate) 59. 6 0 7 l-hydroxy-phenylA-diazo-( i benzene-l-sulfonate) 66. 3 0

Second series of earrperiments Healthy Ill plants 0.1% solutions plants in in per per cent cent 1 H10 35 16 2 l-hydroxy-phenyli-diazo 5'-nitro-benzene-1-sulfonate) 61. 3 0 3 l-hydroxy-phen y1-4-diazo-(4-chloro- 5-m'tro-benzene-1'-sulfonate) 64. 6 0 4 l-hydroxy-phenyli-diazo-(2chloro-3,5-

dinitro-benzene-l-sulfonate) 59. 3 0 5 l-hydroxy-phenyl-4-diazo-(4'-chloro-3,5-

dinitro-benzene-Y-sulionate) 58. 6 0 6 l-hydroxy-phenyli-diazo-(2',4',6-trichloro- 3-nitro-benzene-1-sulfonate) 1 62 0. 3

The preparations are also efiicacious, when used in feebler concentrations.

Third series of erperiments Healthy Ill plants 0.2% solution plants in in per per cent 7 cent 1 H O 52. 3 17 2 Potassium l-hydroxy-benzene-4-diazos11lfonate 72. 3 1. 3

EXAMPLE 4 Seed grains attacked by the winged blight of oats are dipped for 30-minutes into 0.05% solutions of the compounds mentioned below; The results are resumed in the following table:

Attack in Compound per cent H7O Q Calcium 1-l1ydroxybenzenei-diazo-sulfonate Sodium l-hydroxy-2-chloro-benzene-4-diazosulfonate l-hgfgroxg-benZene-4-diaZo-(3',4-dichlorobenzene)- s one 0 l-hydroxl7 zene)-sulfonate EXAMPLE 5 A preparation containing 1% of mercury as methoxyethylmercurysilicate and 12% of potassium 1-hydroxy-2- chloro-phenyl 4 diazosulfonate was tested as seed grain disinfectant in experiments on the field. The following results were obtained:

(1) Stone blight of wheat amino The said preparation is as emcacious as the commercial preparation containing 1.5% of mercury as methoxy-ethylemerouryesilicaile. ,A saving of 33.3 of mercury 'iias-thus been obtained. It has also been examined whether the above preparation impairs the germination of the seed. The respective tests have shown that seed grain is in no way damaged by the treatment.

While we have described our improvements in great detail and with respect toprefenred embodiments thereof, we do not desire to "limit ourselves to such details or embodiments, since many modifications and changes may be made and the invention embodied in widely .difierent forms without departing from the spirit or scope of :the invention in its broadestaspects.

"We claim:

1. Seed fungicidal preparations comprising a substantial quantity .of :an inert solid material and a lesseroquantity of thedouble saltcf ametal salt and .a hydroxy phenyl 'diazonium compound.

.2. The process of rcombatting fungus diseases on seeds and the like which =comprises treating seeds with a composition containin aninertsolid substance and. an active ingredient which is an aromatic diazo compound *selected from the class consisting of aromatic diazoniumsa1ts,aromatic diazotates, aromatic .diazo metal salts, aromatic diazo sulfonates, aromatic :diazo oxides, aromatic diazo amines, and :aromatic diazo imines, the aromatic ring having a phenolic Qhydr xyl group.

8 3. The process as defined in claim 2 wherein the aromatic diazo compound is the double salt ofa metal salt with an aromatic diazonium compound.

4. A seed fungicidal composition comprising "a substantial quantity of asolid inert material and as its active ingredient a lesser quantity wof a compound haWir-rg the formula [HOAr (NN)] If, whereinAr designates an arylene 'radical, "NN is the diazo group, and Y is an N-heteroarw-lene organic radical.

5. The composition \of claim 4 in which the hydroxy-phenyl-rdiazo compound .is ..3.5- dichlor,o- 4ehydroxy-phenyl-diazo-pyrollidide.

(i. The composition of claim 4 in which the hydroxy-i henyl diazo compoi'imi is -3:5-dic-hloroi-hydroxy-phenyl-diazo piperidide.

REFERENCES CITED The following references are of record in the file of this patent:

111NITED :STATES PATENTS Number Name Date 1,919,729 Kharasch Jul y.25 1933 1,982,681 Markush 1380.4, 1984 2,191,259 EPjaff et a1 'Feb..20,, 1949 2,336,308 Smith Dec. *7, aces FOREIGN PATENTS Number Country Date "290,288 Great'Bri-tai-n 1929 OTHER REFERENCES Beilstein, Organische flhemief" Band XVI, 1933, pages 525, 526, and 52-9. {Copy in Patent Ofiice Library...) 

